Nanoscale Size Effects on Push-Pull Fe-O Hybridization through the Multiferroic Transition of Perovskite ϵ-Fe2O3.

Multiferroics have tremendous potential to revolutionize logic and memory devices through new functionalities and energy efficiencies. To reach their optimal capabilities will require better understanding and enhancement of the ferroic orders and couplings. Herein, we use ϵ-Fe2O3 as a model system with a simplifying single magnetic ion. Using 15, 20, and 30 nm nanoparticles, we identify that a modified and size-dependent Fe-O hybridization changes the spin-orbit coupling and strengthens it via longer octahedra chains. Fe-O hybridization is modified through the incommensurate phase, with a unique two-step rearrangement of the electronic environment through this transition with attraction and then repulsion of electrons around tetrahedral Fe. Interestingly, size effects disappear in the high-temperature phase where the strongest Fe-O hybridization occurs. By manipulating this hybridization, we tune and control the multiferroic properties.

Radical Complexes of Nickel(II)/Copper(II) and Redox Non-innocent MB-DIPY Ligands: Unusual Stability and Strong Near-Infrared Absorption at λmax ∼1300†nm.

The preparation of radicals with intense and redox-switchable absorption beyond 1000 nm is a long-standing challenge in the chemistry of functional dyes. Here we report the preparation of a series of unprecedented stable neutral nickel(II) and copper(II) complexes of "Manitoba dipyrromethenes" (MB-DIPYs) in which the organic chromophore is present in the radical-anion state. The new stable radicals have an intense absorption at λmax ∼1300 nm and can be either oxidized to regular [MII (MB-DIPY)]+ (M=Cu or Ni) or reduced to [MII (MB-DIPY)]- compounds. The radical nature of the stable [MII (MB-DIPY)] complexes was confirmed by EPR spectroscopy with additional insight into their electronic structure obtained by UV-Vis spectroscopy, electro- and spectroelectrochemistry, magnetic measurements, and X-ray crystallography. The electronic structures and spectroscopic properties of the radical-based chromophores were also probed by density functional theory (DFT) and time-dependent DFT (TDDFT) calculations. These nickel(II) and copper(II) complexes represent the first stable radical compounds with a MB-DIPY ligand.

Accurate Prediction of Mössbauer Hyperfine Parameters in Bis-Axially Coordinated Iron(II) Phthalocyanines Using Density Functional Theory Calculations: A Story of a Single Orbital Revealed by Natural Bond Orbital Analysis.

Density Functional Theory (DFT) calculations coupled with several exchange-correlation functionals were used for the prediction of Mössbauer hyperfine parameters of 36 bis-axially coordinated iron(II) phthalocyanine complexes with the general formulas PcFeL2, PcFeL'L″, and [PcFeX2]2-, including four new compounds. Both gas-phase and PCM calculations using BPW91 and MN12L exchange-correlation functionals were found to accurately predict both Mössbauer quadrupole splittings and the correct trends in experimentally observed isomer shifts. In comparison, hybrid exchange-correlation functionals underestimated quadrupole splittings, while still accurately predicted isomer shifts. Out of ∼40 exchange-correlation functionals tested, only MN12L was found to correctly reproduce quadrupole splitting trends in the PcFeL2 complexes coordinated with phosphorus-donor axial ligands (i.e., P(OnBu)3 ≈ P(OEt)3 < PMe3 < P[(CH2O)2CH2]-p-C6H4NO2 < PEt3 ≈ PnBu3). Natural Bond Orbital (NBO) analysis was successfully used to explain the general trends in the observed quadrupole splitting for all compounds of interest. In particular, the general trends in the quadrupole splitting correlate well with the axial ligand dependent, NBO-predicted population of the 3dz2 orbital of the Fe ion and are reflective of the hypothesis proposed by Ohya and co-workers ( Inorg. Chem., 1984, 23, 1303) on the adaptability of the phthalocyanine's π-system toward Fe-Lax interactions. The first X-ray crystal structure of a PcFeL2 complex with axial phosphine ligands is also reported.

Simple, Hackable, Size-Selective, Amine-Functionalized Fe-Oxide Nanoparticles for Biomedical Applications.

A facile one-pot method for synthesizing amine-functionalized nonspherical Fe3O4 nanoparticles in gram-scale quantities is presented using just a single source of iron (iron(II) chloride) and an amine (triethylamine). The amine not only transforms iron salt to Fe3O4, but also directs the morphology of the nanoparticles along with the temperature of the reaction and functionalizes them, making the synthesis very economical. By modifying the surface further, these nanoparticles promise to offer useful biomedical applications. For example, after biocide coating, the particles are found to be 100% effective in deactivating methicillin-resistant Staphylococcus aureus (MRSA) bacteria in 2 h. Cellular-uptake studies using biocompatible EDTA-Na3 (N-(trimethoxysilyl-propyl)ethylenediaminetriacetate, trisodium salt)-coated nanoparticles in human glioblastoma U-251 cells show that the majority of the particles are internalized by the cells in the presence of a small dc-magnetic field, making these particles a potential candidate as drug carriers for magnetic field-targeted delivery and hyperthermia.

Direct Synthesis of an Unprecedented Stable Radical of Nickel(II) 3,5-Bis(dimedonyl)azadiisoindomethene with Strong and Narrow Near-Infrared Absorption at λ ∼ 1000 nm.

An unprecedented stable neutral radical nickel(II) complex of 3,5-bis(dimedonyl)azadiisoindomethene (1) was prepared by the direct reaction between 1,3-diiminoisoindoline and dimedone. A new radical complex 1 has an intense and narrow absorption at 1008 nm and can be reduced to a less stable anionic [1]- with a typical aza(dibenzo)boron dipyrromethene (aza-BODIPY) UV-vis spectrum. Complex 1, along with two other colored condensation reaction products 2 and 3, was characterized by spectroscopy and X-ray crystallography, while the paramagnetic nature of 1 was probed by EPR and SQUID methods. Complex 1 forms dimers in the solid state with short (∼3.16 Å) Ni---Ni contacts. Redox data on 1 are indicative of a reversible reduction process in this complex; its magnetism suggests a S = 1/2 state with the spin density delocalized over the aza-BODIPY core. The experimental data 1 and [1]- were correlated with the density functional theory (DFT) and time-dependent DFT calculations.

Biodistribution of negatively charged iron oxide nanoparticles (IONPs) in mice and enhanced brain delivery using lysophosphatidic acid (LPA).

Effective treatment of brain disorders requires a focus on improving drug permeability across the blood-brain barrier (BBB). Herein, we examined the pharmacokinetic properties of negatively charged iron oxide nanoparticles (IONPs) and the capability of using lysophosphatidic acid (LPA) to transiently disrupt the tight junctions and allow IONPs to enter the brain. Under normal conditions, IONPs had a plasma half-life of six minutes, with the liver and spleen being the major organs of deposition. Treatment with LPA enhanced accumulation of IONPs in the brain and spleen (approximately 4-fold vs. control). LPA and IONP treated mice revealed no sign of peripheral immune cell infiltration in the brain and no significant activation of microglia or astrocytes. These studies show improved delivery efficiency of IONPs following LPA administration. Our findings suggest transient disruption of the BBB may be a safe and effective method for increasing IONP delivery to the brain.

Spontaneously formed interfacial metal silicates and their effect on the magnetism of superparamagnetic FeCo/SiO2 core/shell nanoparticles.

The integration of superparamagnetic core/shell nanoparticles into devices and other nanoscale technological applications requires a detailed understanding of how the intimate contact between core and shell nanophases affects the magnetism. We report how, for single-domain FeCo nanoparticles, an FeCo phase unique to the nanoscale with silica shells of increasing thicknesses spontaneously formed interfacial metal silicates between the core and shell (such as Fe2SiO4 and Co2SiO4) and altered the overall magnetism of the nanomaterial significantly. The influence of this previously overlooked phenomenon on magnetic properties is reported. Evidence of these metal silicate interfacial layers was observed by X-ray absorption spectroscopy (XAS) collected over the L3,2 absorption edges of Fe and X-ray photoelectron spectra (XPS) collected over the 2p transitions of Fe and Co. Through the correlation of magnetometry and XPS data, the evolution of nanoparticle magnetic anisotropy is shown to increase with the metal silicate.

Structural Insights into Multi-Metal Spinel Oxide Nanoparticles for Boosting Oxygen Reduction Electrocatalysis.

Multi-metal oxide (MMO) materials have significant potential to facilitate various demanding reactions by providing additional degrees of freedom in catalyst design. However, a fundamental understanding of the (electro)catalytic activity of MMOs is limited because of the intrinsic complexity of their multi-element nature. Additional complexities arise when MMO catalysts have crystalline structures with two different metal site occupancies, such as the spinel structure, which makes it more challenging to investigate the origin of the (electro)catalytic activity of MMOs. Here, uniform-sized multi-metal spinel oxide nanoparticles composed of Mn, Co, and Fe as model MMO electrocatalysts are synthesized and the contributions of each element to the structural flexibility of the spinel oxides are systematically studied, which boosts the electrocatalytic oxygen reduction reaction (ORR) activity. Detailed crystal and electronic structure characterizations combined with electrochemical and computational studies reveal that the incorporation of Co not only increases the preferential octahedral site occupancy, but also modifies the electronic state of the ORR-active Mn site to enhance the intrinsic ORR activity. As a result, nanoparticles of the optimized catalyst, Co0.25 Mn0.75 Fe2.0 -MMO, exhibit a half-wave potential of 0.904 V (versus RHE) and mass activity of 46.9 A goxide -1 (at 0.9 V versus RHE) with promising stability.

Pseudo-octahedral nickel(ii) complexes of strongly absorbing benzannulated pincer-type amido ligands: ligand-based redox and non-Aufbau electronic behaviour.

The synthesis, structures and electronic characterization of three strongly coloured, pseudo-octahedral Ni(ii) complexes supported by redox-active diarylamido ligands featuring benzannulated N-heterocyclic donor arms are reported. The S = 1 paramagnets each present two singly occupied molecular orbitals (SOMOs) identified as metal-based by density functional theory (DFT), consistent with solid-state and solution magnetism measurements. Upon applying oxidative potentials, non-Aufbau behaviour leads to the appearance of intense and well-defined absorption features extending into the near IR (NIR). The attribution of these features to the onset of aminyl radical character through ligand-based redox is corroborated by exceptionally strong intervalence charge-transfer (IVCT) transitions ascribed to electronic communication between two Namido moieties across a Ni(ii) bridge.

Reverse-Engineering Strain in Nanocrystallites by Tracking Trimerons.

Although strain underpins the behavior of many transition-oxide-based magnetic nanomaterials, it is elusive to quantify. Since the formation of orbital molecules is sensitive to strain, a metal-insulator transition should be a window into nanocrystallite strain. Using three sizes of differently strained Fe3 O4 polycrystalline nanorods, the impact of strain on the Verwey transition and the associated formation and dissolution processes of quasiparticle trimerons is tracked. In 40 and 50 nm long nanorods, increasing isotropic strain results in Verwey transitions going from TV ≈ 60 K to 20 K. By contrast, 700 nm long nanorods with uniaxial strain along the (110) direction have TV ≈ 150 K-the highest value reported thus far. A metal-insulator transition, like TV in Fe3 O4 , can be used to determine the effective strain within nanocrystallites, thus providing new insights into nanoparticle properties and nanomagnetism.

Photo-spin-voltaic effect in PtMn/Y3Fe5O12 thin films.

The photo-spin-voltaic effect is revealed by the presence of a spin voltage generated by photons when a non-magnetic metal (e.g., Pt) is in close proximity to a ferrimagnetic insulator (e.g., Y3Fe5O12 (YIG)). This is attributed to the excited electrons and holes diffusing from the proximized layer near the interface to the metallic surface. By using a dual-ion-beam sputtering deposition technique, a metallic PtMn layer was deposited on YIG /Gd3Ga5O12 (GGG) (111) substrates. We report on the photo-induced-spin voltaic effect in a PtMn/YIG/GGG heterostructure. The sign of the photo-generated voltage was found to switch with magnetic field polarity and its intensity to decrease with increasing PtMn thickness. This indicates that spin-polarized electrons are confined near the interface in the metal. Photo-excitation of these carriers, together with spin-orbit coupling with Pt atoms, is at the origin of the measured transverse voltage. The design may find applications in antiferromagnetic spintronics.

Competing ferro- and antiferromagnetic exchange drives shape-selective [Formula: see text] nanomagnetism.

We have synthesized three different shapes of [Formula: see text] nanoparticles to investigate the relationships between the surface Co[Formula: see text] and Co[Formula: see text] bonding quantified by exploiting the known exposed surface planes, terminations, and coordiations of [Formula: see text] nanoparticle spheres, cubes and plates. Subsequently this information is related to the unusual behaviour observed in the magnetism. The competition of exchange interactions at the surface provides the mechanism for different behaviours in the shapes. The cubes display weakened antiferromagnetic interactions in the form of a spin-flop that occurs at the surface, while the plates show distinct ferromagnetic behaviour due to the strong competition between the interactions. We elucidate the spin properties which are highly sensitive to bonding and crystal field environments. This work provides a new window into the mechanisms behind surface magnetism.

Exploiting shape-selected iron oxide nanoparticles for the destruction of robust bacterial biofilms - active transport of biocides via surface charge and magnetic field control.

Biofilms that form on reusable medical devices are a cause of hospital acquired infections; however, sanitization of biofilms is a challenge due to their dense extracellular matrix. This work presents an innovative strategy using biocide-loaded iron oxide nanoparticles transported within the matrix via a magnetic field to eradicate biofilms. Results show that the active delivery of the biocide to underlying cells effectively penetrates the extracellular matrix and inactivates Methicillin resistant Staphylococcus aureus (MRSA) biofilms (responsible for several difficult-to-treat infections in humans). To optimize this treatment, the loading of spherical, cubic and tetrapod-shaped nanoparticles with a model biocide, CTAB (cetyltrimethylammonium bromide) was studied. Biocide loading was determined to be dependent on the shapes' surface charge density instead of the surface area, meaning that biocide attachment is greater for nanoparticles with sharp edges (e.g. cubes and tetrapods). These results can be used to optimize treatment efficacy, and help further understanding of biofilm and nanoparticle surface zeta potentials, and the nanoparticle-biofilm interactions.

Comparative Heating Efficiency of Cobalt-, Manganese-, and Nickel-Ferrite Nanoparticles for a Hyperthermia Agent in Biomedicines.

In this study, the ac magnetic hyperthermia responses of spinel CoFe2O4, MnFe2O4, and NiFe2O4 nanoparticles of comparable sizes (∼20 nm) were investigated to evaluate their feasibility of use in magnetic hyperthermia. The heating ability of EDT-coated nanoparticles which were dispersed in two different carrier media, deionized water and ethylene glycol, at concentrations of 1 and 2 mg/mL, was evaluated by estimating the specific loss power (SLP) (which is a measure of magnetic energy transformed into heat) under magnetic fields of 15, 25, and 50 kA/m at a constant frequency of 195 kHz. The maximum value of SLP has been found to be ∼315 W/g for CoFe2O4 and ∼295 W/g for MnFe2O4 and NiFe2O4 nanoparticles. We report very promising heating temperature rising characteristics of CoFe2O4, MnFe2O4, and NiFe2O4 nanoparticles under different applied magnetic fields that indicate the effectiveness of these nanoparticles as hyperthermia agents.

A new tool to attack biofilms: driving magnetic iron-oxide nanoparticles to disrupt the matrix.

A main feature of biofilms is the self-produced extracellular polymeric substances (EPSs) that act as a protective shield, preventing biocide penetration. We use magnetic iron oxide nanoparticles (MNPs) in combination with magnetic fields to damage the biofilm matrix and cause detachment. A Methicillin-resistant Staphylococcus aureus (MRSA) biofilm strain is used to demonstrate the efficacy of the methodology with different sizes and concentrations of MNPs under AC and DC applied field conditions. We achieve up to a nearly 5 log10 reduction in biofilm bacteria after treatment with 30 mg mL-1 of 11 nm MNPs using a magnetic field. The MNPs cause significant mechanical disruption to the matrix and lead to biofilm dispersal. In addition, using magnetic hyperthermia further affects biofilm damage.

EDTA-Na3 functionalized Fe3O4 nanoparticles: grafting density control for MRSA eradication.

We report a synthesis strategy to simplify often cumbersome post-synthesis ligand exchange protocols and use that approach to synthesize EDTA-Na3 (N-(trimethoxysilylpropyl)ethylenediaminetriacetate, trisodium salt) functionalized hydrophilic and biocompatible Fe3O4 nanoparticles. The grafting density of EDTA-Na3 has been controlled from 0.07-0.37 µmol m-2 by varying the time at which EDTA-Na3 was added to the reaction. The success of EDTA-Na3 surface functionalization has been verified using Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and Mössbauer spectroscopy techniques. Mössbauer spectroscopy results showed the evidence of Fe-EDTA monomer and dimer formation signifying covalent bonding between Fe ions and EDTA-Na3. The earliest addition of EDTA-Na3 resulted in the most stable dispersion of nanoparticles in water and phosphate buffered saline (PBS) which remained stable for more than a month. In addition, our results suggest that these nanoparticles can have useful applications in magnetic hyperthermia and eradication of methicillin-resistant Staphylococcus aureus (MRSA) bacteria in presence of an ac magnetic field.

Iron(II) coordination complexes with panchromatic absorption and nanosecond charge-transfer excited state lifetimes.

Replacing current benchmark rare-element photosensitizers with ones based on abundant and low-cost metals such as iron would help facilitate the large-scale implementation of solar energy conversion. To do so, the ability to extend the lifetimes of photogenerated excited states of iron complexes is critical. Here, we present a sensitizer design in which iron(II) centres are supported by frameworks containing benzannulated phenanthridine and quinoline heterocycles paired with amido donors. These complexes exhibit panchromatic absorption and nanosecond charge-transfer excited state lifetimes, enabled by the combination of vacant, energetically accessible heterocycle-based acceptor orbitals and occupied molecular orbitals destabilized by strong mixing between amido nitrogen atoms and iron. This finding shows how ligand design can extend metal-to-ligand charge-transfer-type excited state lifetimes of iron(II) complexes into the nanosecond regime and expand the range of potential applications for iron-based photosensitizers.

Spin canting across core/shell Fe3O4/MnxFe3-xO4 nanoparticles.

Magnetic nanoparticles (MNPs) have become increasingly important in biomedical applications like magnetic imaging and hyperthermia based cancer treatment. Understanding their magnetic spin configurations is important for optimizing these applications. The measured magnetization of MNPs can be significantly lower than bulk counterparts, often due to canted spins. This has previously been presumed to be a surface effect, where reduced exchange allows spins closest to the nanoparticle surface to deviate locally from collinear structures. We demonstrate that intraparticle effects can induce spin canting throughout a MNP via the Dzyaloshinskii-Moriya interaction (DMI). We study ~7.4 nm diameter, core/shell Fe3O4/MnxFe3-xO4 MNPs with a 0.5 nm Mn-ferrite shell. Mössbauer spectroscopy, x-ray absorption spectroscopy and x-ray magnetic circular dichroism are used to determine chemical structure of core and shell. Polarized small angle neutron scattering shows parallel and perpendicular magnetic correlations, suggesting multiparticle coherent spin canting in an applied field. Atomistic simulations reveal the underlying mechanism of the observed spin canting. These show that strong DMI can lead to magnetic frustration within the shell and cause canting of the net particle moment. These results illuminate how core/shell nanoparticle systems can be engineered for spin canting across the whole of the particle, rather than solely at the surface.

Predicting NOx Catalysis by Quantifying Ce3+ from Surface and Lattice Oxygen.

Our work introduces a novel technique based on the magnetic response of Ce3+ and molecular oxygen adsorbed on the surface of nanoceria and ceria-based catalysts that quantifies the number and type of defects and demonstrates that this information is the missing link that finally enables predictive design of NOx catalysis in ceria-based systems. The new insights into ceria catalysis are enabled by quantifying the above for different ceria nanoparticle shapes (i.e., surface terminations) and O2 partial pressure. We used ceria nanorods, cubes, and spheres and evaluated them for catalytic reduction of NO by CO. We then demonstrated the quantitative prediction of the reactivity of nanomaterials via their magnetism in different atmospheric environments. We find that the observed enhancement of reactivity for ceria nanocubes and nanorods is not directly due to improved reactivity on those surface terminations but rather due to the increased ease of generating lattice defects in these materials. Finally, we demonstrate that the method is equally applicable to highly topical and industrially relevant ceria mixed oxides, using nanoscale alumina-supported ceria as a representative case-a most ill-defined catalyst. Because the total oxide surface is a mixture of active ceria and inactive support and ceria is not likely present as crystallographically well-defined phases, reactivity does not easily scale with surface area or a surface termination. The key parameter to design efficient NO reduction in ceria-based catalysts is knowing and controlling the surface localized excess Ce3+ ion areal density.

Spatially Resolved Large Magnetization in Ultrathin BiFeO3.

Here, a quantitative magnetic depth profile across the planar interfaces in BiFeO3 /La0.7 Sr0.3 MnO3 (BFO/LSMO) superlattices using polarized neutron reflectometry is obtained. An enhanced magnetization of 1.83 ± 0.16 µB /Fe in BFO layers is observed when they are interleaved between two manganite layers. The enhanced magnetic order in BFO persists up to 200 K. The depth dependence of magnetic moments in BFO/LSMO superlattices as a function of the BFO layer thickness is also explored. The results show the enhanced net magnetic moment in BFO from the LSMO/BFO interface extends 3-4 unit cells into BFO. The interior part of a thicker BFO layer has a much smaller magnetization, suggesting it still keeps the small canted AFM state. The results exclude charge transfer, intermixing, epitaxial strain, and octahedral rotations/tilts as dominating mechanisms for the large net magnetization in BFO. An explanation-one suggested by others previously and consistent with the observations-attributes the temperature dependence of the net magnetization of BFO to strong orbital hybridization between Fe and Mn across the interfaces. Such orbital reconstruction would establish an upper temperature limit for magnetic ordering of BFO.